Solar driven semiconductor photocatalytic oxidation is a sustainable environmental remediation method. However, how to design an ideal interface for efficient photogenerated carrier transfer/separation is still the key to improve the photocatalytic performance. To solve this problem, we established a yolk@shell reactor by loading MOF derived ZnO clusters on ultrathin Bi₂MoO₆. The ZnO clusters can enhance the internal electric field and promote the directional migration of charge carriers to limit its recombination. More importantly, the high conductivity polymer PANI is coated to establish a high–speed electron transfer channel in tandem reactor, so that a large amount of carrier is accelerated to surface to participate in the oxidation reaction. The constructed heterojunction has great ability to degrade doxycycline under visible–light with a small amount of catalyst through the S–scheme transfer path. This work provides an important strategy for S–scheme heterojunction efficient carrier transfer and its application in environmental remediation.